Process of producing azo dyestuffs on the fiber



Patented Sept. 13, 1232 Y UNITED STATES- PATENT OFFICE EBWIN HOFFA .ANDCARL SEIB, OF FRANKFORT-ON-THE-MAIN-HOGHST, GERMANY,

.ASSIGNORS '10 GENERAL ANILINE WORKS, INC., 01? NEW YORK, N. Y., ACORPORA- TION OF DELAWARE PROCESS OF PRODUCING AZO DYETUFFS ON TH EFIBER f No Drawing. Application filed June ii, 1928, SerialNo. 288,126,and in Germany June 18, 1927.

Our present invention relates to a process of producing azo dyestuffs onthe fiber.

It is based on the discovery that diazoninm horofluorides as well astetrazoniumborofluor- 8 ides of amines of the aromatic series, includingthose which already possess dyestufl' character, are extremely suitablefor producing dyestufis on the fiber and that dyeings'oi? very goodproperties of fastness are obtained 1 by dyeing or printing by means ofthe said diazonium compounds on vegetable or animal fibers which havebeen pre-treated with any couplin component, for instance a naphthol ora. ody of similar action, such as 2: 3-hydroxynapl1thoic acid arylides,yrazolones, dipyrazolones, acetoacetic (acid ides or diacetoacetic(acid) diaminodiarylcompounds. The dyeings thus obtained are in manycases distinguished by a particular brillianc in comparison with thosewhich are pro need by means of the "usual diazo solutions. r Thefollowing examples illustrate the 1nvention, it being understoodthat-they are in no way limitative: I Example 1.Example for theproduction of the dyestulf from 2:3-hydroxynaphthoicacid-2'-methyl-1-ani1ide and phenyldiazonium horofluoride when thematerial is dyed in lots of 25 kilos, treated with a grounding liquor inthe open vat and subsequently dyed in the tureen.

There is first prepared in a vat holding 50 liters a rounding bathcontaining 7 5 grams of 2: 3- ydroxynaphthoic acid-2-methyl-1- anilideper liter and composed as follows:

3. 75 kilos of 2 -hydr.oxynaphthoic acid-2-methyl-1'- an e 7. 5 litersof 'Turkey red oil of 50 per cent. strength, 5.7 liters of caustic sodasolution of 34 B L0 3. 75 liters of formaldehyde of 33 per centstrength;

made up to 500 liters of liquor.

To this bath is subsequently added for 25 kilos of material to be dyed,0.375 kilos of 2: 3-hydroxynaphthoic acid-2"-methyl-1'-anilide. Theyarns are treated with the grounding liquor for hour and freed fromwater by hydro-extraction.-

For the development of the dyestufl there is used a chassis holding 30liters of liquor,

. which contains 3.85 grams of phenyldia'zonium horofluoride per liter.There is first prepared a bath with 115. 5 grams of phenyldiazoniumborofluoride 1. 5 kilos of sodium chloride 0. 02 liters of acetic acidof 50 per cent. strength,-ma de up to 30 liters of liquor.

To this bath is subsequently added for 26 kilos of material to be dyed,0.300 kilos of phenyldiazonium borofluoride contained in 12.5 liters ofliquor composed as follows:

300 grams of phenyldiazonlum borofiuoride 0. 5 kilo of sodium chloride0. 08 liters pf acetic acid of 50 per cent. strength; made 12. 5 litersof liquor.

The grounded yarns are once passed through the bath in hanks of 1 kilo.

For

every 1 kilo of yarn, liter of additional liquor is to be added. Afterthe development is complete, the material is rinsed several times andsoaped at a temperature of about 60 C.'for hour with 2 grams of soap perliter, finally it is'rinsed and dried. In this manner a vividreddish-orange tint is obtained which is much clearer than that of thedyeing obtainable byusing the phenyldiazonium chloride. The dyestufi hasthe following formula:

Us. bonn Example 2.There .is first prepared in a vat holding 500 litersa grounding bath containing 5 grams of 2:3-hydroxynaphthoicacid-4-chloro-2'-methyl-1'-anilide per liter, the bath being composed of2.5 kilos of- 2:3-hydroxynaphthoic acid-4-chloro-2- methyl-1'-anilide 5liters of Turkey red oil of 50 per cent. strength 5 liters of causticsoda solution of 34 B.

2.5 liters of formaldehyde of 33 per cent. strength;

made up to Y loo ' tained. The dyestufi has For the development of thedyestuif is used First a bath prepared as indicated in Ex ample 1, butinstead of 115.5 grams of phenyldiazonium borofluoride 144 grams oft-chloro- 2-methyl-1-phenyldiazonium borofluoride are used.

Into this bathare subsequently introduced 376 grams of4-chloro-2-methyl-l-phenyldiazonium borofluoride instead of 300 gramsused-in Example '1.

The method of working being the same as that in Example 1, a vividbluish-red is obthe following formula:

By using 5-chloro-2-methyl1-phenyld nium borofluoride a vivid red dyeingis ob tained with a somewhat yellower hue, the dyestufi' having thefollowing formula:

01. QN=N on;

n; H oonncol Example 3.For printing cotton there is first prepared aground ng bath composed of: grams I of 2 3-hydroxynaphthoicacid-4'-ch1oro-2'- methyl-1-anilide grams of monopol soap 1: 1

500 cc. of boiling water cc. of caustic soda solution of 34 36., made upto 1 liter.

The printing paste from 24 grams of4.-chloro-2-metliy1-1-phenyldiazonium borofluoride, which is dissolvedin .thickened with to be used is prepared 476 grams of water, thesolution being grams of tragacanth (100:1000) 1 liter.

The bleached cotton material is padded with the grounding. liquor on asuitable apparatus at a temperature of about35 G. and dried in the hotflue. It is then printed with the printing color and 'after dryingwashed and soaped at boiling temperature. The dyestufl has the followingconstitution:

I Example 4.There is first prepared a grounding bath-having thefollowing ingredients: 1

4. 5 graggil of 12 3-hydroxynapht11oyl-5-chlbro 2'dcoluidine 9 cc. offldrkey red oil of 50 per cent. strength T liter.

to which are finally added 4.5 cc. of formaldehyde of 30 per cent.strength.

the following formula:

cc. of caustlc soda solution of 34 B., made up to 7 The material istreated with this grounding. liquor for -hour. I

There is then prepared a dye-bath as follows:

2. 37 grams of 2-nitrophenyldiazonium borofluoride are made into a pastewith 1.6 cc. of acetic acid 01550 per cent. strength and some warmwater, and the paste is dissolved in 200 cc. 3f grater atv 50-60 C.there are then added a on 250 cc. of sodium chloride solution (1:10) andthe whole is made up to 1 liter.

The material is dyed for hour, then rinsed and soaped at boilingtemperature.

' In this manner a lively bluish-red tint is obtained on the fiber. Thedyestuif has the following formula:

CH: I H0 ONEO-Gl e Example 5.There is first prepared a grounding liquorin the manner stated in Example 4.

The dye-bath is also made up like that of Example 4., except that thereis substituted for the Q-nitrophenyldiazonium borofluoride the samequantity of 4-nitrophenyldiazonium The material is rinsed and soaped ata boiling temperature. Thus a bluish-red dyeing.

is obtained on the fiber. The dyestufii' has the following constitution:v

Example 6.-There is first prepared a grounding-bath with the followingingredients: 5

grams of 2 3-hydroxynaphthoyl-aniline 14 cc. of Turkeyvred oil of 50 percent. strength 10. 5 cc. of caustic soda solution of 34 136., made upto- 1 liter.

to which are finally added 7 cc; of formaldehyde of30 per cent.strength.- The materialis treated with this groundingliquor for A;

Example 7.There is first prepared a Example 9.There is first preparedagrounding bath with the following ingredients:

grams of. 2: 3 -hydroxynaphthoy1- 2' anisidine (OCH',=1) I cc. of Turkered oil of 50 per cent. strength 7. 5 cc. of caust c soda solution of 3436., made up to 1 liter.

to which are finally added 5 cc. of formaldehyde of per cent. strength.The material ihs treated with this grounding liquor for our.

The dye-bath is prepared as described. in

Example 4, except that for 2-nitrophenyldia-f zonium borofluoride thereare substituted 2.75 grams of 2:5-dichloro-4-methylphenyldiazoniumborofluoride' The material is dyed, rinsed and'soaped at boilingtemperature; a vivid scarlet is obtained on the fiber. The lowingformula:

grounding bath having the following ingredients: 3. 5 grazgiglpf21:8-hydroxynaphthoyl-5-chIoro-2-an1sidine 7 cc. of Tiifirey red 011' ofper cent. strength 8. 8 cc. of caustic soda solution of 34 Be., made upto 1 liter.-

to which are finally added 35cc. of formaldehyde of 30 per cent.strength. The material is treated with this grounding liquor for hour. v

The dye-bath is prepared as described in Example 4, but for the2-nitrophenyldiazonium borofluoride there are substituted 2.75

resembles Turkey red. The dyestuif has the following formula:

OH N=N I OOH! H OO.NH O1 dyestuif has the fol-- a diazonium borofluorideof grounding bath having the following ingredientsz 2. 5 grams ofhydroxynaphthoyl l'-naphthylamine v5 cc. of Turkey red oil of 50 percent. strength 7. 5 cc. of caustic soda solution of 34 B., made up to 1liter.

to which are finally added 2.5 cc. of formaldehyde of 30 per cent.strength. The material is treated with this liquor for hour.

The dye-bath is prepared as described in Example 4, but in place of2-nitrophenyldiazonium borofluoride, 1.91 gram of 4:4'-di- (diazoniumborofluoride)-diphenylamine is used. The material is dyed for hour, thenrinsed, acidified with hydrochloric acid, then rinsed cold and hot andsoaped at boiling temperature, whereby a black dyeing is obtained. Thedyestuff has the following formula:

Weclaim: j 1. The process of producing azo dyestuffs on the fiber whichcomprises treating ahydroxynaphthoic acid arylide on the fiber with thefollowing general formula:

. [R-N BF wherein R stands for an aromatic residue.

2. The process of producing azo dyestuffs on the fiber which comprisestreating a hydroxynaphthoic acid 'arylide on the fiber with a diazoniumborofluoride of the following general formula:

wherein It stands for a benzene residue which may be substituted byalkyl, O-alkyl, halogen or the nitro group.

3. The process of producing azo dyestufl's 0 the fiber which comprisestreating a hydroxynaphthoic acid arylide on the fiber with a diazoniumborofluoride of the followiiig general formula:

wherein one X stands for N0 and the other Xs stand. for hydrogen.

4. The process of producing azo dyestuffs on the. fiber which comprisestreating a, hydroxynaphthoic acid arylide on the fiber with a diazoniumborofluoride of the following 7 formula 5. The process of producing anazo dye stufi' on the fiber whlch comprises treating2.3-hydroxynaphthoic acid-2'-n1ethyl-1'-anim lide on the fiber with thediazonium borofluoride of the following formula:

6. The process of producing an azo dyestuff on the fiber which comprisestreating 2.3-hydroxynaphthoic acid-2-methoxy-1'- anilide on the fiberwith the diazoniuin borofluoride of the following formula:

In testimon whereof, we afiix our signa-

